CN1388996A - Proton-conductive electrode, process for producing the same, and electrochemical device - Google Patents

Proton-conductive electrode, process for producing the same, and electrochemical device Download PDF

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CN1388996A
CN1388996A CN01802325A CN01802325A CN1388996A CN 1388996 A CN1388996 A CN 1388996A CN 01802325 A CN01802325 A CN 01802325A CN 01802325 A CN01802325 A CN 01802325A CN 1388996 A CN1388996 A CN 1388996A
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proton
conductive electrode
atom
electrode according
mixture
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CN100459248C (en
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日隈弘一郎
今里峰久
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Sony Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

A proton conducting electrode useful for a fuel battery is provided. The proton conducting electrode is comprised of a mixture including a fullerene derivative and an electron conducting catalyst, wherein the fullerene derivative is composed of carbon atoms forming fullerene molecules and a proton (H<+>) dissociating group introduced into said carbon atoms. This proton conducting electrode is manufactured by coating mixture containing the fullerene derivative and the electron conducting catalyst on a gas transmitting current collector.

Description

Proton-conductive electrode and manufacture method thereof and electrochemical device
Technical field
The present invention relates to a kind of proton (H +) conductive electrode and manufacture method thereof, and the electrochemical device that adopts this proton-conductive electrode.
Background technology
Existing people proposes various electrochemical devices based on hydrogen decomposition reaction or the manufacturing of hydrogen atoms chemical substance, produces proton (H on electrode +) and electronics, proton (H +) and electron reaction generation hydrogen, perhaps proton (H +), electronics and oxygen or another substance reaction produce water or further material, for example fuel cell or other proton type battery, perhaps chemical sensor.
Since in above-mentioned each reaction, relate to electronics, proton and other material, for example hydrogen, oxygen or water, the single site of reaction is being represented in the site compiled of all these materials so.
For example, if the state higher or lower with degree of scatter disposes the catalyst with electronic conductivity on the proton conduction surface, so between proton conduction body and the electronics with and the neighbouring area in the contact point site of representing proton conduction body, electronics and other gaseous matter to exist jointly.In general, such site is called three phase boundary.
Fig. 1 represents the prior art example of electrode structure.In the electrode structure that Fig. 1 represents, the catalyst 3 of performance electronic conductivity is dispersed on the surface of proton conduction body 1, and the surface of rear catalyst is covered by gas permeability collector body 5.Iff being that the surface that has the proton conduction body 1 of dispersion catalyst 3 thereon is used to produce proton (H +) and the reaction of electronics, three phase boundary is present near the contact point of proton conduction body 1 and catalyst 3 so.Yet, all electronics (e -) 4, proton (H +) 8 and the site compiled of gas 6 (for example hydrogen or oxygen) only limit to dotted region, this dotted region works as single three phase boundary, its function as electrode just can not obtain perfect the embodiment as a result.
At present, in order to improve its function as electrode, used a kind of like this technology, this technology comprises the electronic conductivity composition is mixed into electrode material to form three phase boundary on the proton conduction surface, forms certain thickness in entire electrode.
Use this technology, in electrode, form mesh shape electrical conductivity path by catalyst self or by the extra electronic conductivity auxiliary substance that adds in the electrode material, and contained proton conduction body also forms the mesh shape.If other composition except proton and electronics is a gas, electrode itself will be a porous so, to allow gas penetrating in entire electrode.If other composition is not a gas, but solid phase adds electrode with solid phase so.In any of these example, will in entire electrode, form three phase boundary as mentioned above, so that being provided, reflecting point as much as possible improves its electrode function.
Should be noted that in the above-mentioned electrode that is lower than 100 ℃ (comprising room temperature) operation, use proton dissociation liquid or electronic conductivity solid macromolecule electrolyte (for example Nafion, E.I.Du Pont Company make) at present as the proton conduction body that adds electrode.Particularly, because use Nafion, device can solidify, and therefore can be widely used.Therefore, device tends to be widely used as low-temperature fuel cell.
Yet, also run into a problem as the Nafion of solid matter, because its proton conduction mechanism, unless, will can not show its proton conduction performance with the water logging bubble of Nafion itself with capacity.Therefore, if contain Nafion in the electrode, device will be difficult to use continuously in dry air.
Summary of the invention
In view of above-mentioned this area situation, an object of the present invention is to provide a kind of proton-conductive electrode, wherein three phase boundary is present among the electrode galore, and it not only has superiority in its function aspects as electrode, and shows very circlet border dependence; The present invention also provides its manufacture method, and electrochemical device.
For achieving the above object, the invention provides a kind of proton-conductive electrode, form by comprising fullerene (fullerence) derivative and electronic conductivity mixture of catalysts, wherein fullerene derivate is by the proton (H of carbon atom that forms fullerene molecule and the above-mentioned carbon atom of importing +) the group formation of dissociating.
In the present invention, " proton dissociative group " is meant the functional group that can discharge proton when ionization, and " proton (H +) dissociate " be meant separating of when ionization proton and its functional group.
Since proton-conductive electrode of the present invention comprises fullerene derivate and the electronic conductivity catalyst with proton dissociation ability, three phase boundary is present among the electrode with enough amounts, so it have superiority in the function aspects that produces and transmit proton.
Because proton-conductive electrode of the present invention uses fullerene derivate, so it only shows negligible environmental factor dependence, even make the electronic conductivity that it also does well in dry air.Yet it also can use under the situation of humidity.
Adopt a kind of method manufacturing according to proton-conductive electrode of the present invention, the method is included in the mixture that applies fullerene derivate on the gas permeability collector body, and wherein fullerene derivate is made of the proton dissociative group of carbon atom that forms fullerene molecule and the above-mentioned carbon atom of importing.
Since can make by the step that applies said mixture on the gas permeability collector body according to proton-conductive electrode of the present invention, distribution of particles density just can relatively easily obtain adjusting so.And, since mixture can apply with sandwich construction, so just can obtain required thickness.
According to electrochemical device of the present invention, comprise first electrode, second electrode and be clipped in proton conduction body between first and second electrodes, proton-conductive electrode wherein, by comprising fullerene derivate and the electronic conductivity mixture of catalysts is formed, form above-mentioned at least first electrode in the first and second above-mentioned electrodes, wherein fullerene derivate is made of the proton dissociative group of carbon atom that forms fullerene molecule and the above-mentioned carbon atom of importing.
In according to electrochemical device of the present invention, can realize outstanding current density and output characteristic,
Wherein at least the first electrode in first and second electrodes is constructed by proton-conductive electrode, and proton-conductive electrode comprises fullerene derivate and catalyst.
Electrochemical device of the present invention not necessarily needs humid air, even this makes the performance that it also does well in dry air, and can use continuously.
By reading embodiment of the present invention as shown in the drawing, other purpose of the present invention, characteristics and advantage will be more apparent.
The accompanying drawing summary
Fig. 1 is the schematic cross sectional view that the traditional electrode of proton conduction body is adopted in expression.
Fig. 2 A and Fig. 2 B represent C respectively 60And C 70Molecular structure.
Fig. 3 A and Fig. 3 B represent the structure as the fullerene poly hydroxide of the typical fullerene derivate that uses among the present invention.
Fig. 4 A and Fig. 4 B are the schematic diagrames of the example of expression fullerene derivate.
Fig. 5 and 6 is schematic diagrames of the example of the proton conduction body that uses among the present invention of expression.
Fig. 7 is the schematic diagram of an example of the proton conduction body that uses among the present invention of expression.
Fig. 8 illustrates the structure of employing according to the fuel cell of proton-conductive electrode of the present invention.
Fig. 9 A and Fig. 9 B represent the equivalent-circuit component that uses in embodiment of the present invention.
Figure 10 is the curve chart of expression element complex impedance comparative result.
Figure 11 is the temperature dependent curve chart of expression element proton conduction body.
Figure 12 represents to adopt the generating result according to the fuel cell of proton-conductive electrode of the present invention.
The preferred version that carries out an invention
Describe the present invention in detail referring now to the preferred embodiment of the invention.
Will import wherein matrix as the proton dissociative group that uses among the present invention, fullerene molecule will not be had particular restriction, as long as they are spherical bunch shape molecules.Yet, be selected from C 14, C 60(referring to Fig. 2 A), C 70(referring to Fig. 2 B), C 76, C 78, C 80, C 82Or C 84Fullerene molecule itself or two or more mixture of these fullerene molecules normally preferred.
These fullerene molecules are open (Kroto, H.W. in the mass spectrum of bunch bundle of carbon laser cutting in 1985; Heath J.R.; O ' brien, S.C.; Curl, R.F.; Smalley, R.E.Nature1985.318,162).In fact the preparation method established after 5 years.That is,, find preparation method, and from that time, fullerene has caused extensive attention as the semi-conducting material of carbon containing by the arc discharge method of carbon electrode 1990.
The inventor has carried out a lot of researchs to the electronic conductivity of fullerene molecule derivative, and find, the fullerene poly hydroxide that obtains by the composition carbon atom that oh group is imported fullerene shows high electronic conductivity at large-temperature range very, comprise ambient temperature range, promptly at least 160 ℃--40 ℃ temperature range comprises the solidifying point and the boiling point of water.Find that in addition when the hydrogen sulfate ester group was imported the composition carbon atom substituted hydroxy group of fullerene, its proton conduction body became outstanding.
More specifically, as shown in Fig. 3 A and Fig. 3 B, fullerene poly hydroxide is the generic term by fullerene and the compound that additional plural oh group constitutes on it, and so-called richness is reined in alcohol (fullerenol).Certainly, the number of oh group or its arrangement can change with a lot of double recipe formulas in the molecular structure.Richness is reined in the synthetic example of alcohol and was delivered (Chiang, L.Y. in 1992 for the first time by Chiang etc.; Swirczewski, J.W.; Hsu, C.S.; Chowdhury, S.K.; Cameron, S.; Creegan, K., J.Chem.Soc., Chem.Commu.1992,1791).From that time, have and rein in alcohol with the richness that imports oh group wherein than the more quantity of preset value wherein and caused extensive attention, especially for its water-soluble; And mainly obtain research in biological association area.
As schematically showing among Fig. 4 A, the inventor has made richness rein in alcohol and has formed polymer, and interaction will produce between contiguous richness is reined in the oh group of pure molecule like this, represent with zero in the drawings; And find that for the first time, this polymer shows high electronic conductivity, in other words, H +The phenolic hydroxyl group group of reining in pure molecule from richness with the visible amount of macroscopic view dissociates.
Purpose of the present invention except richness is reined in alcohol, also can be used to have plural number-OSO 3The fullerene polymer of H group is made the proton conduction body and is realized.Fullerene poly hydroxide, as shown in Fig. 4 B, wherein-OSO 3The H group has replaced the OH group, and promptly sulfuric acid hydrogen ester type richness is reined in alcohol, also by Chiang etc. at 1994 report (Chiang, L.Y.; Wang, L.Y., Swirczewski, J.W.; Soled, S.; Cameron, S., J.Org.Chem.1994,59,3960).Should be noted that to have only-OSO 3This group of H group or plural number and the centre of oh group each, also can be included in sulfuric acid hydrogen ester type richness and rein among the molecule of alcohol.
As for the proton conduction body, on the basis that a large amount of said derivatives is gathered into massive material, prove, proton from great amount of hydroxy group group intrinsic in the fullerene molecule or-OSO 3The H group is participated in directly mobilely, makes and needn't for example catch from the hydrogen or the proton of water vapour molecule from atmosphere, needn't absorb water particularly, to used atmospheric gas without limits from extraneous supplementing water.On the other hand, form the fullerene performance electrophilic characteristic on the basis of these derivative moleculars, this point be considered to highly acidic-OSO 3The improvement of the hydrionic ionization in H group and the oh group is extremely important.This is the reason of the outstanding electronic conductivity of proton conduction body of the present invention.
And, since the great amount of hydroxy group group and-OSO 3The H group can import a fullerene molecule, and the proton density that participates in the conduction of per unit volume conductor so will increase to some extent.This is the conductive reason of the existing effect of proton conduction body surface of the present invention.
The major part of proton conduction body of the present invention is made of the carbon atom of fullerene, makes that it is in light weight, not perishable and does not contain polluter.The manufacturing cost of Fullerece also reduces greatly.Therefore, consider the energy, environment and economic worth, fullerene is considered to than other similar material more near the carbonaceous material of ideal material.
Our research discloses, will proton dissociative group be limited in aforementioned oh group or-OSO 3The H group.
Therefore, if with-XH represents this group that dissociates, and X is atom or the atomic group with two valence links, and Here it is so fully.Equally, if with-OH or-YOH represents this group, and Y is atom or the atomic group that has two valence links arbitrarily, this also is sufficient.
Particularly, except-OH ,-OSO 3H, proton dissociative group also can be-COOH ,-SO 3H or-PO (OH) 2In any one.
For synthesizing according to the fullerene derivate that uses in the proton-conductive electrode of the present invention, so long as pass through with the known process technology, for example acid treatment or hydrolysis, be applied to the fullerene molecule powder, any suitable proton dissociative group is imported the composition carbon atom of fullerene molecule, is exactly sufficient.
According to the present invention, comprise preferably porous of fullerene derivate and electronic conductivity mixture of catalysts, preferably porosity rate is in the scope of 1-90%.This makes gas can be diffused into entire electrode, so that form the quantity of three phase boundary with the increase reflecting point in entire electrode, thereby improves the function of electrode aspect generation and transmission proton.
Comprise that the weight mixing ratio of fullerene derivate and catalyst is 1 in fullerene derivate and the electronic conductivity mixture of catalysts: 100-100: 1.
And, mixture preferably with form of single sheet at the gas permeability collector body, for example form on the carbon paper.Mixture can be used as individual layer or exists with sandwich construction.
As shown in Fig. 5 and 6, as mentioned above, to form by the gas permeability collector body according to proton-conductive electrode of the present invention, the mixture of being made up of fullerene derivate and electronic conductivity catalyst on it forms the single or multiple lift structure.
In the proton-conductive electrode shown in Fig. 5, comprise richness and rein in the porous mixture of pure molecule 2 as fullerene derivate and electronic conductivity catalyst 3, disperse to be coated on the surface of proton conduction body 1, the surface of porous mixture covers with gas permeability collector body 5 then.
On the other hand, the proton-conductive electrode shown in Fig. 6 obtains by the porous mixture of reining in pure molecule 2 and electronic conductivity catalyst 3 with multi-layer coated richness.
The proton-conductive electrode of the present invention that constitutes as shown in Fig. 5 and 6 uses and comprises the porous mixture that richness is reined in pure molecule 2 and electronic conductivity catalyst 3, makes that gas can be penetrating in entire electrode.And, since reining in pure molecule 2, richness has the proton dissociation ability as fullerene derivate, and electronic conductivity catalyst 3 forms in entire electrode, three phase boundary 7 not only forms near the contact point between proton conduction body 1 and the catalyst 3 so, and forms near the contact point between catalyst 3 and the Fu Le alcohol molecule 2.These three phase boundaries 7 are electronics (e -) 4, proton (H +) 8 and the site all compiled simultaneously of gas 6 (for example hydrogen or oxygen).
Because proton-conductive electrode of the present invention can not only be near the contact point between proton conduction body 1 and the catalyst 3 and can form three phase boundary 7 near the contact point between catalyst 3 and the Fu Le alcohol molecule 2, so electrode can be improved in the function that produces and transmit aspect the proton.In addition, because proton-conductive electrode contains the fullerene derivate with proton dissociation ability, so electrode can use in dry air continuously.
The catalyst of the formation porous mixture that uses in the proton-conductive electrode of the present invention is preferably formed by the porous mass that carries the electronic conductivity atom.In this case, the amount of the entrained electronic conductivity atom of porous mass 1-50wt% preferably.
The atom (catalytic metal) of performance electronic conductivity can be platinum, ruthenium, vanadium, tungsten or its mixture, and porous mass can be carbon dust, porous Ni-Cr agglomerated material, Al 2O 3Agglomerated material or porous Li-Cr alloy sheets.In these materials, the combination of platinum and carbon dust is preferential.
Preferably, electronic conductivity is with 0.1-10mg/cm 2Amount be present between proton conduction body 1 and the gas permeability collector body 5.
Can be used for various electrochemical devices and have its advantage according to proton-conductive electrode of the present invention.Promptly comprising first and second electrodes and be clipped in the basic structure of the proton conduction body between these electrodes, at least the first electrode in first and second electrodes can be to adopt proton-conductive electrode of the present invention.
Adopt proton-conductive electrode of the present invention can be used for electrochemical device, wherein at least one in first and second electrodes is gas electrode.
Adopt the fuel cell of proton-conductive electrode of the present invention will obtain subsequently explaining.
The proton conduction mechanism of fuel cell of the present invention is represented in the schematic diagram of Fig. 7.Proton conduction unit 9 is clipped between first electrode 10 (for example hydrogen electrode) and second electrode 11 (for example oxygen electrode), and the proton (H that dissociates +) shown in arrow in the accompanying drawing, move to second electrode 11 from first electrode 10.
Fig. 8 represents to adopt the typical fuel cells according to proton-conductive electrode of the present invention.As shown in Figure 8, this fuel cell comprises negative electrode 10, at one end has terminal 15, and it uses according to proton-conductive electrode of the present invention; And positive electrode 11, at one end having terminal 16, it also uses proton-conductive electrode.Negative electrode 10 constitutes the fuel electrodes or the hydrogen utmost point, and positive electrode 11 constitutes oxygen electrode.Simultaneously, and nonessential use proton-conductive electrode of the present invention as positive electrode 11.Negative electrode 10 and positive electrode 11 are arranged in parallel to each other face-to-face, and as shown in Figure 8, proton conduction unit 9 is clipped between negative electrode 10 and the positive electrode 11.
When using the fuel cell that constitutes as shown in Figure 8, hydrogen act as inlet 17 transmission of fuel 19 by negative electrode 10 places, so that it is in outlet 18 discharges, this not necessarily.By the 17 supplied fuel (H that enter the mouth 2) 19 producing proton when the runner 20, the proton that produces in proton that these protons produce in negative electrode 2 and the proton conduction unit 9 moves to positive electrode 11, herein proton with from entering the mouth 21 to runner 22 supply oxygen (gas) 24 reactions, and be sent to exhaust outlet 23 thus, so produced required electromotive force.
For the fuel cell of the present invention that constitutes as shown in Figure 8, use proton-conductive electrode of the present invention, proton is at negative electrode 10 internal disintegrations, and when proton dissociates in proton conduction unit 9, move to positive electrode 11 from the proton of negative electrode 10, thereby improved electronic conductivity.Therefore, use fuel cell of the present invention, do not need damping device, the system that makes obtains simplifying and having alleviated weight, and the function of electrode, for example current density or output characteristic can improve.
In adopting electrochemical device of the present invention such as fuel cell, the proton conduction body that is clipped between the proton-conductive electrode is not particularly limited, can uses any suitable material, such as, for instance, fullerene hydroxide, sulfuric acid hydrogen ester type richness are reined in alcohol or Nafion.
Now explain embodiments of the invention in detail.
Embodiment
Synthesizing of fullerene poly hydroxide
This synthetic list of references (Chiang, L.Y. of using; Wang, L.Y., Swirczewski, J.W.; Soled, S.; Cameron, S., J.Org.Chem.1994,59,3960) carry out.With 2g C 60/ C 70The fullerene mix powder is added in the 30ml fuming sulfuric acid, stirs 3 days in nitrogen, and simultaneous temperature remains on 60 ℃.The material of gained slowly is added in the Anaesthetie Ether that cools off in the ice bath.Centrifugation gained precipitation, it is inferior to give a baby a bath on the third day after its birth with Anaesthetie Ether, and washes twice with 2: 1 mixtures of Anaesthetie Ether and acetonitrile, dry under 40 ℃ of low pressure.Desciccate is added in the 60ml deionized water, and in 85 ℃, under with the situation of nitrogen air-blowing, stirred 10 hours.By centrifugal, reaction product isolated from precipitation, precipitation is washed several, repeated centrifugation and dry under 40 ℃ of low pressure with pure water.The brown powder of gained is carried out FF-IR to be measured.Measure discovery by this, the IR spectrum and the C of brown powder 60(OH) 12Approximate unanimity, thereby the explanation powder be object fullerene poly hydroxide powder.More than reaction is with C 60As follows for representing:
The preparation of fullerene poly hydroxide aggegation tablet
Get 90mg fullerene poly hydroxide powder, it is pressed into diameter 15mm circular tablet to a direction.The pressure of this moment approximately is 5 tons/cm 2Find that fullerene poly hydroxide powder plasticity under the situation that does not contain adhesive resin or similar substance is very strong, can form highly stable tablet.About 300 μ m are thick for this tablet, are called the aggegation tablet of fullerene poly hydroxide.
Synthesizing of fullerene poly hydroxide sulfuric acid hydrogen ester (full esterification)
The above-mentioned list of references of this synthetic use carries out.1g fullerene poly hydroxide powder is added in the 60ml fuming sulfuric acid, in nitrogen, under room temperature, stirred 3 days.The reactant of gained slowly is added in the Anaesthetie Ether that cools off in the ice bath.Centrifugation gained precipitation, it is inferior to give a baby a bath on the third day after its birth with Anaesthetie Ether, and washes twice with 2: 1 mixtures of Anaesthetie Ether and acetonitrile, dry under 40 ℃ of low pressure.The brown powder of gained is carried out FF-IR to be measured.Measure discovery by this, the IR spectrum of the compound that the IR spectrum of brown powder and its all oh groups all become the sulfuric acid hydrogen ester is similar to consistent, this the same with shown in the above-mentioned reference material, thus the explanation powder is an object fullerene poly hydroxide sulfuric acid hydrogen ester.
More than reaction is with C 60(OH) 12Following for representing (identical hereinafter):
The preparation of fullerene poly hydroxide sulfuric acid hydrogen ester aggegation tablet
Get 70mg fullerene poly hydroxide powder, it is pressed into diameter 15mm circular tablet to a direction.The pressure of this moment approximately is 5 tons/cm 2Find that fullerene poly hydroxide powder plasticity under the situation that does not contain adhesive resin or similar substance is very strong, can form highly stable tablet.About 300 μ m are thick for this tablet, are called the aggegation tablet of fullerene poly hydroxide sulfuric acid hydrogen ester.
The preparation of the aggegation fullerene tablet of comparative example
For relatively, get the 90mg fullerene that is used as synthetic parent material among the embodiment of front, to a direction it is pressed into diameter 16mm circular tablet.The pressure of this moment approximately is 5 tons/cm 2Find that powder plasticity under the situation that does not contain adhesive resin or similar substance is very strong, can form highly stable tablet.About 300 μ m are thick for this tablet, are called the tablet of comparative example.
Embodiment (the aggegation tablet of fullerene poly hydroxide sulfuric acid hydrogen ester) and comparative example The measurement of the electronic conductivity of tablet
Conductibility for the tablet of measuring embodiment and comparative example is clipped in every kind of tablet between a pair of aluminium sheet, and tablet and aluminium sheet diameter respectively are 15mm.Combination applies the alternating voltage that amplitude 0.1V, frequency change from 7MHz to 0.01Hz to each tablet, the complex impedance when measuring each frequency.Measurement is carried out under dry air.
In impedance measurement, as shown in Fig. 9 A, the proton conduction unit 9 of the proton conduction body that is made of tablet of above-mentioned embodiment has constituted equivalent circuit capacitance, and constitute to cross over electric capacity 14a, the 14b of first and second electrodes 10,11, and proton conduction unit 9 is connected representative by resistance 4 and electric capacity 5 parallel.Simultaneously, electric capacity 13 represents that proton moves delays effect (high-frequency phase retardation), and the parameter that on behalf of proton, resistance 12 move.
Complex impedance Z is by Z=Re (Z)+iIm (Z) representative.Accounting is by the frequency dependence of the proton conduction unit of above-mentioned equivalent electric circuit representative.
Fig. 9 B is illustrated in the equivalent electric circuit under the situation of common fullerene molecule that use do not have the proton dissociation characteristic, in above-mentioned comparative example.Among Fig. 9 B, 9a represents the fullerene unit.
Figure 10 represents the impedance measurements of tablet in embodiment and the comparative example.
As can be seen from Figure 10, the response of the frequency response of complex impedance and capacitor itself basic identical (as shown in Figure 10 B), and the conduction behavior of the charged particle of the agglutination body of fullerene itself such as electronics or ion is not observed.On the contrary, in an embodiment, as shown in Figure 10 A, can partly observe extraordinary semi arch, although some is flat in high-frequency.This shows, has some conduction behaviors of charged particle in the tablet.In addition, also can notice rapid rising in the imaginary part of low frequency range impedance.This shows that when near direct voltage, the blocking-up of aluminium electrode charged particle occurs.Since aluminium electrode side charged particle is natural electronics, as can be seen, the charged particle in the tablet is the particle except that electronics or ion.Rein in the structure of alcohol from used richness and judge that charged particle must be a proton.
Can obtain the conductibility of charged particle from the X-shaft section of the electric arc observed facing to high frequency side.In the tablet of embodiment, can calculate it and be about 5 * 10 -6S/cm.Can draw, the agglutination body of this fullerene derivate allows the proton conduction under dry air, the room temperature condition.
Use the tablet (the aggegation tablet of fullerene poly hydroxide sulfuric acid hydrogen ester) of embodiment, at 160 ℃--the measurement of carrying out above-mentioned complex impedance in 40 ℃ the temperature range is to verify the conductive temperature dependency of observing from high frequency side electric arc.The result represents with Arrhenius plot that in Figure 11 therefrom as can be seen, in the temperature range from 160 ℃ to-40 ℃ of variations, conductibility is linear change.In brief, this figure shows that the single ionic conduction mechanism is carried out in the said temperature scope.That is to say that the agglutination body of the fullerene derivate that uses among the present invention allows to comprise room temperature than the proton conduction in the large-temperature range, particularly even the proton conduction when allowing 160 ℃ of high temperature or-40 ℃ of low temperature.
The manufacturing of the fuel cell of embodiment and comparative example and generating test
Carbon dust (the mean particle size: 50nm) mix and sneak in oxolane (THF) solution that will contain 20wt% platinum with the weight ratio of the fullerene poly hydroxide sulfuric acid hydrogen ester powder that obtains as mentioned above with 1: 2.The mixture of gained is coated on the carbon paper, and making platinum containing amount is 1mg/cm 2, rein in pure electrode to form the thick richness that contains of the present invention of 50 μ m.
Make two richnesses that contain of the present invention and rein in the electrode of alcohol and contain the fuel cell device of these electrodes with formation, these electrodes are positioned at the film of fullerene derivate powder agglutination body, and (thickness: both sides 25 μ m) are as the proton conduction body.This fuel cell device is assembled in shown in Fig. 8 in the cell of fuel cell.One side (negative side) and the opposite side (side of the positive electrode) of fuel cell device shown in Fig. 8 are exposed to respectively in dry hydrogen and the dry oxygen with the test of at room temperature generating electricity.
For comparative example, use Nafion solution, (mean particle size: 50m) be coated on the carbon paper, making platinum containing amount is 1mg/cm will to contain the carbon dust of 20wt% platinum 2, Nafion measures 2mg/cm 2To make Nafion mixture electrode.
Make the electrode of two Nafion mixtures and be placed on the film that contains the fullerene derivate powder that (thickness: both sides 25 μ m) to be making fuel cell device, and fuel cell device is assembled in shown in Fig. 8 in the cell of fuel cell.One side (negative side) and the opposite side (side of the positive electrode) of fuel cell device shown in Fig. 8 are exposed to respectively in dry hydrogen and the dry oxygen with the test of at room temperature generating electricity.
The result of each generating test represents in Figure 12.
These results show, when the open voltage of embodiment and comparative example all is 1.2V, use the rich embodiment that reins in the alcohol mixture electrode to show the feature shown in the A among Figure 12.That is to say that compare with the comparative example of the Nafion mixture electrode shown in the B among Figure 12, embodiment improves, and has superiority aspect output characteristic aspect current density.
Industrial application
Because proton-conductive electrode of the present invention is fullerene derivate and electronic conductivity catalysis The mixture of agent, wherein fullerene derivate is by the carbon atom that forms fullerene molecule with import it In proton dissociative group consist of, three phase boundary just can be present in the amount of abundance in the electrode, Therefore electrode has superiority in the function aspects that produces and transmit proton.
And, because proton-conductive electrode uses fullerene derivate, its environmental factor dependence Low, even can be in dry air use continuously, so that it can show electrochemical device is required Outstanding electronic conductivity.
To using the electrochemical device according to proton-conductive electrode of the present invention not have environment Restriction so system just can reduce its size and simplify its structure, so just might be developed Optimum current density and output characteristics.

Claims (46)

1. proton-conductive electrode, by comprising fullerene derivate and the electronic conductivity mixture of catalysts is formed, wherein fullerene derivate is by the carbon atom that forms fullerene molecule with import the proton (H of above-mentioned carbon atom +) the group formation of dissociating.
2. proton-conductive electrode according to claim 1, wherein said proton dissociative group is-XH, and X is the atom with two valence links, H is a hydrogen atom.
3. proton-conductive electrode according to claim 1, wherein said proton dissociative group be-OH or-YOH, and Y is atom or the atomic group with two valence links.
4. proton-conductive electrode according to claim 3, wherein said proton dissociative group be selected from-OH ,-OSO 3H ,-COOH ,-SO 3H and-PO (OH) 2
5. proton-conductive electrode according to claim 1, wherein said mixture is a porous.
6. proton-conductive electrode according to claim 1, wherein said mixture are the single or multiple lift structures.
7. proton-conductive electrode according to claim 1, wherein said mixture forms with stratiform on the gas permeability collector body.
8. proton-conductive electrode according to claim 1, wherein said catalyst carry the porous mass of the atom of performance electronic conductivity.
9. proton-conductive electrode according to claim 1, the weight mixing ratio of fullerene derivate described in the wherein said mixture and catalyst is 1: 100-100: 1.
10. proton-conductive electrode according to claim 1, wherein said mixture has the porosity rate of 1-90%.
11. proton-conductive electrode according to claim 7, wherein the gas permeability collector body is a carbon paper.
12. proton-conductive electrode according to claim 8, wherein the electronic conductivity atom is a platinum, and described porous mass is a carbon dust.
13. proton-conductive electrode according to claim 8, the amount of the electronic conductivity atom that wherein said porous mass carries are 1-50 weight %.
14. proton-conductive electrode according to claim 8, wherein the electronic conductivity atom is with 0.1-10mg/cm 2Amount be present on the described gas permeability collector body.
15. proton-conductive electrode according to claim 1, wherein said fullerene molecule are spherical carbon bunch Cm molecules, m=36 wherein, 60,70,76,78,82,84 etc.
16. a method of making proton-conductive electrode may further comprise the steps:
Apply fullerene derivate and electronic conductivity mixture of catalysts on the gas permeability collector body, wherein fullerene derivate is made of the proton dissociative group of carbon atom that forms fullerene molecule and the above-mentioned carbon atom of importing.
17. proton-conductive electrode according to claim 16, wherein said proton dissociative group is-XH, and X is the atom with two valence links, and H is a hydrogen atom.
18. proton-conductive electrode according to claim 16, wherein said proton dissociative group be-OH or-YOH, and Y is atom or the atomic group with two valence links.
19. proton-conductive electrode according to claim 16, wherein said proton dissociative group be selected from-OH ,-OSO 3H ,-COOH ,-SO 3H and-PO (OH) 2
20. proton-conductive electrode according to claim 16, wherein said mixture is a porous.
21. proton-conductive electrode according to claim 16, wherein said mixture applies with the single or multiple lift structure.
22. proton-conductive electrode according to claim 16, wherein said catalyst carry the porous mass of the atom of performance electronic conductivity.
23. proton-conductive electrode according to claim 16, the weight mixing ratio of fullerene derivate described in the wherein said mixture and catalyst is 1: 100-100: 1.
24. proton-conductive electrode according to claim 16, wherein said mixture has the porosity rate of 1-90%.
25. proton-conductive electrode according to claim 16, wherein the gas permeability collector body is a carbon paper.
26. proton-conductive electrode according to claim 22, wherein the electronic conductivity atom is a platinum, and described porous mass is a carbon dust.
27. proton-conductive electrode according to claim 22, the amount of the electronic conductivity atom that wherein said porous mass carries are 1-50 weight %.
28. proton-conductive electrode according to claim 22, wherein the electronic conductivity atom is with 0.1-10mg/cm 2Amount be present on the described gas permeability collector body.
29. proton-conductive electrode according to claim 16, wherein said fullerene molecule are spherical carbon bunch Cm molecules, m=36 wherein, 60,70,76,78,82,84 etc.
30. electrochemical device, comprise: first electrode, second electrode and be clipped in proton conduction body between first and second electrodes, proton-conductive electrode wherein, by comprising fullerene derivate and the electronic conductivity mixture of catalysts is formed, at least form above-mentioned first electrode in above-mentioned first and second electrodes, wherein fullerene derivate is made of the proton dissociative group of carbon atom that forms fullerene molecule and the above-mentioned carbon atom of importing.
31. electrochemical device according to claim 30, wherein said proton dissociative group is-XH, and X is the atom with two valence links, and H is a hydrogen atom.
32. electrochemical device according to claim 30, wherein said proton dissociative group be-OH or-YOH, and Y is atom or the atomic group with two valence links.
33. electrochemical device according to claim 30, wherein said proton dissociative group be selected from-OH ,-OSO 3H ,-COOH ,-SO 3H and-PO (OH) 2
34. electrochemical device according to claim 30, wherein said mixture is a porous.
35. electrochemical device according to claim 30, wherein said mixture applies with the single or multiple lift structure.
36. electrochemical device according to claim 30, wherein said mixture forms with stratiform on the gas permeability collector body.
37. electrochemical device according to claim 30, wherein said catalyst carry the porous mass of the atom of performance electronic conductivity.
38. electrochemical device according to claim 30, the weight mixing ratio of fullerene derivate described in the wherein said mixture and catalyst is 1: 100-100: 1.
39. electrochemical device according to claim 30, wherein said mixture has the porosity rate of 1-90%.
40. electrochemical device according to claim 30, wherein the gas permeability collector body is a carbon paper.
41. according to the described electrochemical device of claim 37, wherein the electronic conductivity atom is a platinum, and described porous mass is a carbon dust.
42. according to the described electrochemical device of claim 37, the amount of the electronic conductivity atom that wherein said porous mass carries is 1-50wt%.
43. according to the described electrochemical device of claim 37, wherein the electronic conductivity atom is with 0.1-10mg/cm 2Amount be present on the described gas permeability collector body.
44. electrochemical device according to claim 30, wherein said fullerene molecule are spherical carbon bunch Cm molecules, m=36 wherein, 60,70,76,78,82,84 etc.
45. electrochemical device according to claim 30, at least one in wherein said first and second electrodes is gas electrode.
46. according to the described electrochemical device of claim 45, wherein this device manufactures fuel cell.
CNB018023258A 2000-08-08 2001-08-07 Proton-conductive electrode, process for producing the same, and electrochemical device Expired - Fee Related CN100459248C (en)

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